Apparatus and method for sampling

ABSTRACT

In various embodiments of the invention, a cargo container can be monitored at appropriate time intervals to determine that no controlled substances have been shipped with the cargo in the container. The monitoring utilizes reactive species produced from an atmospheric analyzer to ionize analyte molecules present in the container which are then analyzed by an appropriate spectroscopy system. In an embodiment of the invention, a sorbent surface can be used to absorb, adsorb or condense analyte molecules within the container whereafter the sorbent surface can be interrogated with the reactive species to generate analyte species characteristic of the contents of the container.

CLAIM OF PRIORITY

The present application is a continuation of and claims priority to (1)U.S. patent application Ser. No. 15/495,246 entitled “APPARATUS ANDMETHOD FOR SAMPLING OF CONFINED SPACES” by Inventor Brian D. Musselman,filed Apr. 24, 2017, which is a continuation of and claims priority to(2) U.S. patent application Ser. No. 15/081,459 entitled “APPARATUS ANDMETHOD FOR SAMPLING OF CONFINED SPACES” by Inventor Brian D. Musselman,filed Mar. 25, 2016, which issued Apr. 25, 2017 as U.S. Pat. No.9,633,827; which is a continuation of and claims priority to (3) U.S.patent application Ser. No. 14/493,231 entitled “APPARATUS AND METHODFOR SAMPLING OF CONFINED SPACES” by Inventor Brian D. Musselman, filedSep. 22, 2014 which issued Jul. 12, 2016 as U.S. Pat. No. 9,390,899;which is a continuation of and claims priority to (4) U.S. patentapplication Ser. No. 14/279,644 entitled “APPARATUS AND METHOD FORSAMPLING OF CONFINED SPACES” by Inventor Brian D. Musselman, filed May16, 2014, which issued Nov. 25, 2014 as U.S. Pat. No. 8,895,916; whichis a continuation of and claims priority to (5) U.S. patent applicationSer. No. 13/831,957 entitled “APPARATUS AND METHOD FOR SAMPLING OFCONFINED SPACES” by Inventor Brian D. Musselman, filed Mar. 15, 2013,which issued May 20, 2014 as U.S. Pat. No. 8,729,496; which is acontinuation of and claims priority to (6) U.S. patent application Ser.No. 13/530,387 entitled “SAMPLING OF CONFINED SPACES” by Inventor BrianD. Musselman, filed Jun. 22, 2012, which issued Oct. 22, 2013 as U.S.Pat. No. 8,563,945; which is a continuation of and claims priority to(7) U.S. patent application Ser. No. 12/776,034 entitled “SAMPLING OFCONFINED SPACES” by Inventor Brian D. Musselman, filed May 7, 2010,which issued Jun. 26, 2012 as U.S. Pat. No. 8,207,497; which claimspriority to (8) U.S. Provisional Patent Application No. 61/176,860entitled “MATERIAL COLLECTOR AND PORTABLE IONIZER FOR REMOTE SAMPLING OFCONFINED SPACES” by Inventor Brian D. Musselman, filed May 8, 2009, thecontents of each of (1)-(8) are incorporated herein by reference intheir entireties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is related to the following applications:

-   (8) U.S. Utility patent application Ser. No. 11/580,323, entitled “A    SAMPLING SYSTEM FOR USE WITH SURFACE IONIZATION SPECTROSCOPY” by    Brian D. Musselman, filed Oct. 13, 2006 which issued Apr. 20, 2010    as U.S. Pat. No. 7,700,913;-   (9) U.S. Utility patent application Ser. No. 11/754,115, entitled    “HIGH RESOLUTION SAMPLING SYSTEM FOR USE WITH SURFACE IONIZATION    TECHNOLOGY” by Brian D. Musselman, filed May 25, 2007, which issued    Aug. 17, 2010 as U.S. Pat. No. 7,777,181;-   (10) U.S. Utility patent application Ser. No. 11/754,158, entitled    “APPARATUS FOR HOLDING SOLIDS FOR USE WITH SURFACE IONIZATION    TECHNOLOGY” by Brian D. Musselman, filed May 25, 2007 which issued    May 11, 2010 as U.S. Pat. No. 7,714,281;-   (11) U.S. Utility patent application Ser. No. 11/754,189, entitled    “FLEXIBLE OPEN TUBE SAMPLING SYSTEM FOR USE WITH SURFACE IONIZATION    TECHNOLOGY” by Brian D. Musselman, filed May 25, 2007 which issued    Apr. 27, 2010 as U.S. Pat. No. 7,705,297;-   (12) U.S. Utility patent application Ser. No. 11/872,666, entitled    “SAMPLING SYSTEM FOR CONTAINMENT AND TRANSFER OF IONS INTO A    SPECTROSCOPY SYSTEM” by Brian D. Musselman, filed Oct. 15, 2007,    which issued Apr. 19, 2011 as U.S. Pat. No. 7,928,364; and-   (13) U.S. Utility patent application Ser. No. 12/275,079, entitled    “SAMPLING SYSTEM FOR USE WITH SURFACE IONIZATION SPECTROSCOPY” by    Brian D. Musselman, filed Nov. 20, 2008, which issued Sept. 27, 2011    as U.S. Pat. No. 8,026,477.

These related applications (8)-(13) are herein expressly incorporated byreference in their entireties.

FIELD OF THE INVENTION

The present invention relates to rapid, remote sampling of analyte ionsin confined spaces.

BACKGROUND OF THE INVENTION

A shipping container can be used for transporting machinery, equipmentand produce. They are designed and built to carry heavy loads andsupport heavy loads, even when they are stacked on top of each other.They tolerate harsh environments when they are transported globally.Most shipping containers are made to the same standard measurements (8′width, 20′, 35′, 40′ or 45′ length and 8′6″ or 9′6″ height). They caninclude top, side and bottom rails with interval stringers in betweenthe top and bottom rails and doors at one end. As many as 30 intervalstringers can be present in a 40′ container to help prevent delaminationof the outer container coating from the container frame. As a result thecontainers can be structurally very strong and when empty can be stackedupon each other up to twelve high.

A drum, or more specifically a 55-gallon drum (or 44-gallon drum basedon the imperial volume) is another commonly used container for shippingmaterials. A 55-gallon drum is 22.5 inches (572 mm) in diameter and 33.5inches (851 mm) high as specified in ANSI MH2 and has a volume ofapproximately 208-liters. A 42 gallon (159 liter) and 25 gallon (95liter) drum are also common size containers used for shipping. A drumshipping container can be closed-head or open-head. Closed-head drumsare generally made of a steel cylinder with reinforcing rings to improverigidity and durability. Bottom and top plates can be welded to thecylinder. The reinforcing rings are positioned at the bottom, one third,two thirds and top. The top plate has one 2-inch (50.8 mm) NPT and one¾-inch (19 mm) NPT threaded holes or bungs. These are generally onopposite sides. This arrangement is echoed in many plastic drums of thesame size. Various components can be mounted to the drum, such as drumpumps and bung mixers. They are commonly used for transporting oils,fuels and a variety of chemicals. Open-head drums are sealed by aconcave inwards mechanical ring clamp that can make an airtight sealagainst a gasket. Top plates exist with standard bung holes. Open-headdrums can be used to ship many non-volatile liquids as well asindustrial powders (e.g., aluminum), beads (e.g., polystyrene) andgranules (e.g., fertilizers).

SUMMARY OF THE INVENTION

The rapid determination of the composition of an analyte inside aconfined container and in particular a shipping container is of interestto national security. In various embodiments of the invention, acontainer can be monitored at appropriate time intervals to determinewhether any and which controlled substances have been shipped in thecontainer. In an embodiment of the invention, a sorbent surface can beused to sample the contents of the container and an atmospheric analyzercan be used to ionize analyte species (AS) including molecules orfragments present on the sorbent surface which are then analyzed by anappropriate spectroscopy system.

In an embodiment of the invention, a sorbent surface can be used toabsorb, adsorb or condense analyte molecules within the container whereafter the sorbent surface can be interrogated with the reactive species(RS) to generate analyte species (AS) characteristic of the contents ofthe container. In an embodiment of the invention, a plurality of sorbentmaterials located in a container can be simultaneously and/orsequentially exposed to the atmosphere in the container and absorb,adsorb or condense analyte molecules onto the sorbent surface, where theanalyte molecules are characteristic of the contents of the container.In various embodiments of the invention, movement of the air within thecontainer to either an area where the RS are present or to the sorbentmaterial can be facilitated. Over an interval of time, the sorbentmaterial can be subjected to analysis either while fixed in situ and/orafter removal of the sorbent material. Analysis can include exposure ofthe sorbent material to RS produced by an atmospheric ionizer in orderto ionize the analyte molecules present on the sorbent materialgenerating AS and then transfer of the AS to a spectroscopic analysisand detection system.

BRIEF DESCRIPTION OF THE DRAWINGS

Various embodiments of the present invention will be described in detailbased on the following figures, wherein:

FIG. 1 is a schematic diagram of an atmospheric ionizer in which theentrance is closed for analysis;

FIG. 2A is a schematic diagram of an embodiment of the invention with anatmospheric ionizer directed at an atmospheric ionizer sorbent material(atmosphere AISM) in which the entrance is open for collection ofchemical traces, where the ionizer and AISM are located in a confinedspace of the container;

FIG. 2B is a schematic diagram of an embodiment of the invention wherethe AISM, but not the atmospheric ionizer is located in a confined spaceof the container;

FIG. 2C is a schematic diagram of an embodiment of the invention wherethe AISM and the atmospheric ionizer are located outside the confinedspace of the container;

FIG. 3 is a schematic diagram of an embodiment of the invention with anatmospheric ionizer and an AISM where the ionizer and AISM are locatedin a container;

FIG. 4 is a schematic diagram of an embodiment of the invention showingan AISM which can be inserted into a container where the sorbentmaterial is in contact with air in the container where multipleatmospheric ionizers can be directed at the sorbent material, where themultiple atmospheric ionizers and the AISM are located in a container;

FIG. 5 is a schematic diagram of the containment tube according to anembodiment of the invention; and

FIG. 6 is a flow diagram showing the use of an AISM installed in a cargocontainer according to an embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Abbreviations include:

AISM=atmospheric ionization sorbent material; API=atmospheric pressureionization; AS=analyte species; DESI=desorption electrospray ionization;DMS=differential mobility spectrometer; GIS=gas ion separator; IMS=ionmobility spectrometer; MS=mass spectrometry; RS=reactive species.

Definitions of certain terms that are used hereinafter include:

The transitional term “comprising” is synonymous with “including,”“containing,” or “characterized by,” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified in the claim, but does not exclude additionalcomponents or steps that are unrelated to the invention such asimpurities ordinarily associated with a composition.

The transitional phrase “consisting essentially of” limits the scope ofa claim to the specified materials or steps and those that do notmaterially affect the basic and novel characteristic(s) of the claimedinvention.

The term Gas-Ion Separator (GIS) will be used to refer to a device whichseparates ions from one or both neutral molecules and neutral atomsallowing the pre-concentration and transfer of the ions to an analysissystem. The term ‘inlet tube’ will be used to refer to the low vacuumside of a GIS. The term ‘outlet tube’ will be used to refer to the highvacuum side of the GIS. The term ‘contained tube’ will be used to referto a tube present in the container (that can be concealed) that normallyfunctions to sample the atmosphere at different locations in thecontainer. In various embodiments of the invention, the contained tubecan be an inlet tube. Active ionization refers to the process where anatmospheric analyzer not utilizing a radioactive nucleus can be used toionize analyte ions. Passive ionization refers to any process where aradioactive nuclei results in analyte ions. A capacitive surface is asurface capable of being charged with a potential. A surface is capableof being charged with a potential, if a potential applied to the surfaceremains for the typical duration time of an experiment, where thepotential at the surface is greater than 50% of the potential applied tothe surface. A vacuum of atmospheric pressure is approximately 760 torr.Generally, ‘approximately’ in this pressure range encompasses a range ofpressures from below 10¹ atmosphere=7.6×10³ torr to 10⁻¹atmosphere=7.6×10¹ torr. A vacuum of below 10⁻³ torr would constitute ahigh vacuum. Generally, ‘approximately’ in this pressure rangeencompasses a range of pressures from below 5×10⁻³ torr to 5×10⁻⁶ torr.A vacuum of below 10⁻⁶ torr would constitute a very high vacuum.Generally, ‘approximately’ in this pressure range encompasses a range ofpressures from below 5×10⁻⁶ torr to 5×10⁻⁹ torr. In the following, thephrase ‘high vacuum’ encompasses high vacuum and very high vacuum.

Cargo is any product to be shipped. Shipping means any transportation ofa container including by ship, by plane, by space craft, by rail, bytruck and by car. Loading a cargo includes placing, filling ordispensing a cargo in a container. Closing a container includes non-airtight sealing and air tight sealing. En route analysis includes anyanalysis of the AISM or the sorbent surface after the cargo has beenloaded but before the cargo has been unloaded. Delivery means thearrival of the cargo container at any destination port and/orintermediate port. Port means any destination location. Unloading cargomeans any removal of the cargo from the container. Initiation means anyprocess that allows the prior exposure of the AISM to be substantiallyreduced or eliminated.

A. Active Ionization DESI

Desorption ElectroSpray Ionization (DESI) is an atmospheric ionizer ofanalytes. DESI occurs when a gas under high pressure is use to project astream of highly charged liquid particles onto a surface in order todesorb ions at atmospheric pressure into the space above the surface.Thus, DESI utilizes a liquid to complete the desorption ionization. Thedesorbed ions can be pulled into the vacuum envelope of a massspectrometer inlet for subsequent mass determination or ion mobilitydetermination. In these circumstances, the transfer of ions into theinlet of the MS relies in large part on the action of the vacuum to drawthe ions into the MS inlet. MS sources often contain multiple pumpingstages separated by small orifices, which serve to reduce the gaspressure along the path that the ions of interest travel to anacceptable level for mass analysis; these orifices also operate as ionfocusing lenses when an electrical potential is applied to theirsurface.

DART®

DART® is another atmospheric ionization method suitable for the analysisof analytes. Various embodiments of DART® are described in U.S. Pat. No.7,112,785 to Laramee (hereinafter referred to as the '785 patent) whichare herein expressly incorporated by reference in their entireties. The'785 patent is directed to desorption ionization of molecules fromsurfaces, liquids and vapor using a carrier gas containing reactivespecies (RS). The DART® atmospheric ionizer can use a large volume ofcarrier gas, e.g., helium is suitable although other inert gases thatcan generate RS can be used.

Nitrogen DART

An atmospheric ionizer can ionize analyte molecules without the use ofsolvents to dissolve the analyte. The ionization occurs directly fromsolids and liquids. Molecules present in the gas phase can also beionized by the reactive species exiting the atmospheric ionizer. In anembodiment of the invention, the reactive species utilized can beexcited nitrogen atoms or molecules. In an embodiment of the invention,the reactive species can produce long lived metastables to impact theanalyte molecules at atmospheric pressure and effect ionization.

The recent commercialization of a DART® atmospheric ionizer withincreased capability for functioning with naturally abundant nitrogen asthe metastable carrier gas is a significant advance. This can enable theutilization of the DART® atmospheric ionizer in more diverse climates,and with minimal requirement for compressed gases or any liquidscommonly used with alternative atmospheric ionization systems. In anembodiment of the invention, processing of ambient air to remove theoxygen can be accomplished by placing a tube containing an oxygenscavenger in the path of gas flow from the air to the inlet of the DART®atmospheric ionizer. An oxygen absorbent (see U.S. Pat. No. 4,127,503 toYoshikawa et al., which is incorporated by reference in its entirety)such as a mixture of finely divided moist Fe₂O₃ and KCl can be used toreduce the level of oxygen present in an air stream. In an alternativeembodiment of the invention, a process for separating air by cryogenicdistillation (U.S. Pat. No. 7,219,514 to Gamier et al., which isincorporated by reference in its entirety) using an apparatus comprisinga medium-pressure column and a low-pressure column that are thermallycoupled, where a quantity of compressed and purified air is cooled in anexchange line down to a cryogenic temperature and is sent at leastpartly to the medium-pressure column, and a nitrogen-enriched stream issent from the medium-pressure column to the low-pressure column and thenitrogen-enriched stream can be withdrawn from the low-pressure column.In another embodiment of the invention, an oxygen absorbent can be usedin combination with cryogenic distillation to further reduce the levelof oxygen present in the nitrogen-enriched stream or more efficientlyreduce the level of oxygen. An atmospheric ionizer therefore can be anideal device for sampling of confined spaces into which introduction ofsolvents to mix with analytes might create an unstable chemicalcondition.

Sampling Different Areas and Compartments

As shown in FIG. 5, in various embodiments of the invention, one or morecontainment tubes are used to allow diverse and/or large volumes of thecontainer to be sampled. The proximal end of the containment tube 52 isclosest to the position being sampled and the distal end of thecontainment tube 52 can be directed onto the sorbent surface (notshown). In FIG. 5, the containment tube 52 spans a partition 36separating compartments in the container 144 by passing through the subfloor 146 above the sub floor support 148 of the container 144. Invarious embodiments of the invention, by embedding the containment tubeinto the container during construction of the container, the possibilityof tampering with or otherwise interfering with the detection system canbe reduced. In addition to a sub floor, a shipping container can containa number of structural features including top, side and bottom railswith interval stringers in between the top and bottom rails and doors atone end. As many as 30 interval stringers can be present in a 40′. Ashipping drum can also contain a number of structural features includingreinforcing rings positioned at the bottom, one third, two thirds andtop. In addition, a shipping container in the shape of a drum generallycontains a seam running from the bottom plate to the top plate.

In an embodiment of the invention, the containment tubing can be made ofone or more materials selected from the group consisting of stainlesssteel, non-magnetic stainless steel, steel, titanium, metal, flexiblemetal, ceramic, silica glass, plastic and flexible plastic. In anembodiment of the invention, the containment tubing can range in lengthfrom 10 millimeters to 10 meters. In an embodiment of the invention, thecontainment tubing can be made of non-woven materials. In an embodimentof the invention, the containment tubing can be made from one or morewoven materials.

In various embodiments of the invention, the one or more containmenttubes can be hidden in any of these structural features. In variousembodiments of the invention, the containment tube can be positionedwithin the container framework during construction of the container,including positioning of the one or more of the rails, stringers andreinforcing rings. The proximal end of the containment tube can exit thecontainer framework so that the atmosphere at this location can besampled. The distal end of the containment tube can exit the containerframework and can be directed at the AISM. A vacuum can be employed todraw vapor from the regions of the container where the proximal end ofthe containment tube is positioned. The positions where the containmenttubes exit the container framework can be concealed such that tamperingwith the containment tube can require detailed drawings or electronicsensors to locate the containment tube exit points. In addition, ‘dummy’exit points can be introduced into the design to mask the location ofreal exit points. The ‘dummy’ exit points can hide the true exitlocation point and make tapering with the true exit points moreproblematic. The containment tube running throughout a portion of thecontainer frame can also be concealed with foam. Foam can also be usedas part of the container optimized insulation system. By disguising exitpoints, attempts to tamper with, restrict or otherwise block thecontainment tube can be minimized. By measuring the background in thecontainer from a number of different points a more through examinationof container content can be carried out. Measurement of the backgroundcan also be used to determine whether any of the containment tube exitpoints have undergone tampering.

Gas-Ion Separator (GIS)

In various embodiments of the invention, devices and methods fortransferring analyte ions desorbed from the sorbent surface using anatmospheric analyzer into the inlet of a mass spectrometer can utilize aGas-Ion Separator (GIS). Embodiments of this invention include devicesand methods for collecting and transferring analyte ions and/or otheranalyte species formed within a carrier to the inlet of a massspectrometer.

In an embodiment of the invention, one or both the inlet and the outletGIS tubing can be made of one or more materials selected from the groupconsisting of stainless steel, non-magnetic stainless steel, steel,titanium, metal, flexible metal, ceramic, silica glass, plastic andflexible plastic. In an embodiment of the invention, the GIS tubing canrange in length from 10 millimeters to 10 meters. In an embodiment ofthe invention, the GIS tubing can be made of non-woven materials. In anembodiment of the invention, the GIS tubing can be made from one or morewoven materials.

In various embodiments of the invention, a GIS comprising two or moreco-axial tubes with a gap between the tubes and a vacuum applied in thegap region is used to allow large volumes of carrier gas to be sampled.In various embodiments of the invention, a GIS is made up of an inlettube and an outlet tube. In an embodiment of the invention, the proximalend of the inlet tube is closest to the sorbent surface and the distalend of the inlet tube can be some distance away from the proximal endwhere a vacuum can be applied. In various embodiments of the invention,the proximal end of the outlet tube is adjacent the distal end of theinlet tube and the distal end of the outlet tube enters the spectroscopysystem. In various embodiments of the invention, by embedding the inlettube in the container during construction of the container, thepossibility of tampering with or otherwise interfering with the GIS canbe reduced. A shipping container can include top, side and bottom railswith interval stringers in between the top and bottom rails and doors atone end. As many as 30 interval stringers can be present in a 40′. Ashipping drum can contain reinforcing rings positioned at the bottom,one third, two thirds and top.

In various embodiments of the invention, a GIS inlet tube can becontained within the container framework including one or more of therails, stringers, reinforcing rings and seams. The GIS inlet tube can beused to transfer ions formed at the sorbent surface to a spectroscopysystem. The proximal end of the GIS inlet tube can exit the containerframework to sample the ions formed at the sorbent surface. In variousembodiments of the invention, the distal end of the GIS inlet tube canexit the container framework at a position to couple with the GIS outlettube where a vacuum can be applied. In various embodiments of theinvention, the distal end of the GIS inlet tube can exit the containerframework at a site and couple with a second GIS inlet tube, wherein theGIS outlet tube and vacuum can be applied at a location distal to thesite. The positions where the GIS inlet tube exits the containerframework can be concealed such that tampering with the GIS inlet tubecan require detailed drawings or electronic sensors to locate the GISinlet tube exit points. In addition, ‘dummy’ GIS inlet tube exit pointscan be introduced into the design to mask the location of real exitpoints. The ‘dummy’ exit points can hide the true exit point locationand make tapering with the true exit points more difficult. The GISinlet tube running throughout a portion of the container frame can beconcealed with foam. Foam can also be used as part of the containeroptimized insulation system. By disguising exit points, attempts totamper with, restrict or otherwise block the GIS inlet tube can beminimized.

An atmospheric ionizer (such as DART®, DESI or other ambient pressuredesorption ionization source) can generate ions at atmospheric pressurewith the AISM sample surface at near ground potential. In an alternativeconfiguration the sample surface can have an applied electric potential.As shown in FIG. 1 an atmospheric ionizer 100 can include the housing103, an entry port 121 for introducing the carrier gas 122, an electrode111 connected to a power supply 112 that supplies a potential differencebetween the electrode 111 and a counter electrode 147 that is sufficientto produce an electrical discharge which creates RS which subsequentlypass and traverse through the length of the housing 103 through the exitgrid 135 and thereby exit the atmospheric ionizer. In the case ofdesorption/ionization with an atmospheric ionizer there are situationsin which there is no component of the system to which an electricalpotential can be applied in order to selectively focus ions towards themass spectrometer inlet. The process of desorption/ionization in theseinstances relies in large part on the action of the vacuum to draw theions into the inlet of either the mass spectrometer (MS), ion mobilityspectrometer (IMS) or differential mobility spectrometer (DMS).

Sorbent Material

Sampling inside confined spaces such as containers can involve captureof chemical containing atmosphere from the inside of the container andanalysis of the captured atmosphere using appropriate chemical analysistechniques. Alternatively, the atmosphere can be sampled over aprolonged period by introducing a sorbent material into the confinedspace. Accordingly, the sorbent material can then be withdrawn outsidethe container and analysis carried out of the sorbent material usingappropriate chemical analysis techniques. The chemical analysis caneither be carried out on-site or sent to a remote laboratory for bothidentification and quantification of the threat posed by those chemicalsprior to allowing the distribution of the contents of the confined spaceor the cargo of the container beyond the port area. However, thesetechnologies suffer from the drawbacks that are resultant uponwithdrawing a sample from the container and carrying out analysis ofthat sample. These drawbacks include the contamination of the samplesubsequent to separation of the sample from the container, samplesabotage for example to cover narcotics interdiction efforts, sampletampering for example to cover illegal activity such as smuggling,increased background and increased probability of sampling error.

In an embodiment of the present invention, a sorbent material is used tosample the atmosphere within the confined space of a container over aninterval of time. The sorbent material is subsequently subjected toanalysis either while fixed in place in the container location or afterremoval from the container location. Analysis can include exposure ofthe sorbent material to a reactive species (RS) in order to ionizeanalyte species (AS) present on the sorbent material and transfer the ASto an analytical spectroscopy detection system.

In an embodiment of the invention, collection of chemical vapors foranalysis in a confined space can be carried out by using a sorbentmaterial such as but not limited to Tenax, silica gel, charcoal, aluminaand more recently fullerenes. In various embodiments of the invention, awide variety of chemical analysis methods can utilize various solventsto enable trace detection of substances of interest. In an alternativeembodiment of the invention, sorbent materials can be chemicallymodified to permit enhanced capability for retention of specific analytemolecules or classes of chemicals thereby improving the potential fordetection of those analyte molecules. In an embodiment of the invention,a sorbent material can be heat stable to permit reuse. In an alternativeembodiment of the invention, a sorbent material can be consumed in theprocess of the analysis. In the case of desorption ionization at ambientpressure the sorbent material provides a substrate for the desorptionionization event when it is positioned at the distal end (i.e., infront) of the atmospheric ionizer or in contact with the gas exiting theatmospheric ionizer. In an embodiment of the invention, the sorbentmaterial can be derivatized with a specific reactive group to react withspecific analyte molecules of interest (e.g., reaction of surfaceimpregnated potassium chloride with volatile nitrate to form nitrosylchloride). In an alternative embodiment of the invention, the sorbentmaterial can be derivatized with a reactive metal such as gold to form areactive surface for a general analyte molecule of interest.

AISM

In an embodiment of the invention, the combination of an atmosphericionizer integrated with an Atmospheric Ionization Sorbent samplingModule (AISM) provides capability for rapid and long duration monitoringof container contents. As shown in FIG. 2A the AISM 200 includes asorbent material 210 and a gas ion separator (inlet tube only is shown)259 located inside the container. In an embodiment of the presentinvention, the AISM 200 can be positioned internal to the container 230being analyzed. In an embodiment of the invention, an atmosphericionizer 100 can also be positioned internal to the container 230 beinganalyzed. The atmospheric ionizer 100 includes a housing 103, an entryport 121, a power supply 112 that supplies a potential differencebetween the electrode 111 and a counter electrode 147 that is sufficientto produce an electrical discharge which creates RS which subsequentlypass and traverse through the length of the housing 103 and afterexiting the grid 135 are directed onto the sorbent material 210. In analternative embodiment of the invention, as shown in FIG. 2B anatmospheric ionizer 100 can be positioned external to the container 230while the sorbent material 210 and GIS 259 are within the container. Theatmospheric ionizer 100 includes a housing 103, an entry port 121, apower supply 112 that supplies a potential difference between theelectrode 111 and a counter electrode 147 that is sufficient to producean electrical discharge which creates RS which subsequently pass andtraverse through the length of the housing 103 and after exiting thegrid 135 are directed onto the sorbent material 210 located inside thecontainer 230. The atmospheric ionizer 100 passes thru the container ata hole or bung 245.

In another alternative embodiment of the present invention, shown inFIG. 2C the AISM 200 can be positioned external to the container 230being analyzed. In this embodiment the sorbent material 210 and theinlet tube of a GIS 259 can be positioned outside of the container 230(where one or both the AISM 200 and the sorbent material 210 can beisolated from the atmosphere, not shown in FIG. 2C). The atmosphereinside the container 230 can be introduced to the sorbent material 210in the isolated atmosphere through a tube 240. In this embodiment, theatmospheric ionizer 100 can also be positioned external to the container230 and directed onto the sorbent material 210. By positioning the AISMexternally, 55-gallon drum containers and other size containers forshipping liquids can be monitored. By removing one of the bungs 246 onthe top of the container 230 or through another entry point, the AISMcan be connected through a tube 240 to the container 230. The AISM canremain attached to the container for a sufficient period of time inwhich the AISM monitors the contents. The atmospheric ionizer 100includes a housing 103, an entry port 121, a power supply 112 thatsupplies a potential difference between the electrode 111 and a counterelectrode 147 that is sufficient to produce an electrical dischargewhich creates RS which subsequently pass and traverse through the lengthof the housing 103 and after exiting the grid 135 are directed onto thesorbent material 210 located outside the container 230. The analytespecies AS formed from molecules absorbed, adsorbed or condensed on thesorbent material 210 can then be directed into a spectrometer foranalysis.

In an alternative embodiment of the invention, the AISM can be detachedfrom the container and sent to a facility for analysis. At the facilitythe AISM is connected to the atmospheric ionizer 100 and an analyzer.The analyte species AS formed from molecules absorbed, adsorbed orcondensed on the sorbent material 210 can then be directed into thespectrometer for analysis.

In an embodiment of the invention, AISM can provide for the rapidinspection of the container contents. In an embodiment of the invention,AISM can be operated robotically or in an automated fashion and withoutoperator intervention to minimize operator exposure or danger to thecontents of the container. In an embodiment of the invention, the AISMsorbent material can be in air contact or otherwise exposed to theinternal contents of the container. In various embodiments of theinvention, vapors can adsorb, absorb, condense or otherwise be capturedon the sorbent material over time by controlling its temperature. In analternative embodiment of the invention, internal tubing can beintegrated into the container construction or otherwise utilized toallow collection of vapor from remote or segmented areas of thecontainer. In an embodiment of the invention, a fan can be used to drawambient air through the tubing so that it can be introduced to theheadspace immediately adjacent to the sorbent material. In an embodimentof the invention, air can be re-circulated through the volume of thecontainer. In an embodiment of the invention, the recirculation canprovide for repetitive exposure of the sorbent to any volatile moleculesassociated with the container contents. As shown in FIG. 6, the AISM canbe installed in (or on) a container 600. The cargo can already be loadedor subsequently be loaded onto the container 610. The door, opening orentry way for loading the cargo can then be closed 620. The monitoringusing the AISM can then be initiated 630. Initiation can involvestarting the fan to flow air through the container, unsealing oruncovering the sorbent material and/or regenerating the sorbentmaterial. The cargo container is then shipped to a destination 640.Before reaching the destination, the AISM can be analyzed en route 650.Provided analysis reveals no restricted substance is present in thecargo, the cargo container is delivered to the destination 660. Thecargo can then be unloaded from the container 670. The cargo containeris then available for loading of a new cargo and shipment 680. The AISMcan be replaced or regenerated to monitor the new cargo to be loaded.

FIG. 3 shows an embodiment of the invention where the temperature of thesorbent material is controlled by a temperature controller 320. In anembodiment of the invention, the temperature controller 320 attached tothe sorbent material 210 can be used to cryogenically cool the sorbentmaterial in order to increase the condensation of molecules on thesorbent surface. In an alternative embodiment of the invention, thetemperature controller 320 can heat the sorbent material 210 to effectdesorption of condensed molecules from the sorbent. In an embodiment ofthe invention, by heating the sorbent material, adsorbed and/or absorbedmolecules can be desorbed off the surface or from within the volume ofthe sorbent material for analysis. After analysis allowing the sorbentmaterial to cool down in an inert environment results in theregeneration of the sorbent material 210, the AISM 300 can be reused.Alternatively, the AISM can be heated directly prior to use as aninitiation step. Once the AISM has cooled down, it can begin collection.In an embodiment of the invention, the AISM 300 with regenerated sorbentmaterial 210 can be used to continue monitoring or to begin monitoringthe fresh contents of the container. Connecting pathways or tubes 310allow the atmosphere in different regions 311, 312 of the containers tocontact the sorbent material 210. In various embodiments of theinvention, the AISM 300 with an atmospheric ionizer 100 includes anentry port for introducing the carrier gas 122, a power supply 112 thatsupplies a potential difference between electrodes to produce anelectrical discharge and a GIS 259 (inlet tube only shown). The AISM 300and atmospheric analyzer 100 can be positioned in the container housingby sliding the AISM 300 into a receptacle or port so that the distal endof the atmospheric ionizer 100 can introduce RS to the sorbent material210. In such a configuration when the container is transported to a portof entry or is in transit to a port of entry, insertion of the AISM 300attached to electrical and gas connections can be used to activate andanalyze the sorbent material 210. In an alternative embodiment of theinvention, when the container enters a port of entry the atmosphericionizer and ancillary equipment are connected to the AISM 300 afterremoval of the AISM from the container.

FIG. 4 shows an embodiment of the invention where multiple atmosphericionizers 100 are directed to the one or more sorbent material 210.Vapors from different regions of the container can be transported to thesorbent material through tube 310 which can be connected to a pluralityof tubes the distal ends of which are open to the atmosphere thuspermitting collection and transfer of atmospheric molecules fromdifferent regions of the container 311 and 312. The sorbent material 210may be segmented into distinct regions each of which can be controlledby the temperature controller 320 which can also be segmented in orderto provide the means to collect both low and high vapor pressuremolecules from the same container for analysis. Multiple atmosphericionizers 100 can be used in order to analyze different sections of thesegmented sorbent material 210 with excited species generated atdifferent temperatures or with different reagent species 122, 123. In anembodiment of the invention, a chemical signature is impregnated onto asorbent material 210 as a means to confirm the integrity of the sorbentmaterial 210. One or more of the multiple atmospheric ionizers 100 canbe used in order to verify the integrity of the AISM module 300. Precisepositional alignment between one or more atmospheric ionizers 100 andthe GIS inlet tube can also be used to verify that the AISM 300 has notbeen tampered with or otherwise disabled. Precise positional alignmentof one or more components of a chemical code in a chemical code patterncan be used to verify that the AISM 300 has not been tampered with orotherwise disabled.

In an embodiment of the invention, the AISM 300 is sealed to preventexposure of the sorbent material 210 to ambient air during its transportor insertion into a container. In an embodiment of the invention, uponinsertion into a container the AISM 300 is configured to permit exposureof the sorbent material 210 to the ambient atmosphere of the containerthus beginning the sampling process. In an embodiment of the invention,the AISM 300 is designed to be placed in an enclosure embedded in theside of the container. In an alternative embodiment of the invention,the AISM 300 is designed to be suspended by a tether in a container. Inanother embodiment of the invention, the AISM 300 is designed to befixed as an appendage in a container. In various other embodiments ofthe invention, the AISM 300 is otherwise configured in such a manner soas to permit the flow of gas from the container through a portion of thesampling module containing the sorbent material 210.

In an embodiment of the invention, during transport of the container itcan be desirable to sample the contents of the container in a rapidmanner without removing the AISM 300. In an embodiment of the invention,after transport of the container it can be desirable to sample thecontents of the container in a rapid manner without removing the AISM300. The advantage of sampling a container with robotic control or froma remote location is the interdiction of controlled substances beforethey pose an actual threat. By sampling a container ship on the high seaor at least before entry into port, explosive or lethal chemicalbiological and radiological threats can be addressed in a safer manner.The ability to expose different areas of an AISM 300 or differentsorbent surfaces over time allows for compensation of backgroundreadings. The ability to sample from different compartments of acontainer onto different areas of an AISM 300 or different sorbentmaterial 210 surfaces over time allows for analysis of the integrity ofthe whole system. Attempts to stop the flow of air from one compartmentcan be revealed by comparative analysis of that compartment with anothercompartment onto separate areas of an AISM 300 and/or comparison overtime.

In an embodiment of the invention, radiological threats can bedetermined by using the GIS interface without turning on an atmosphericionizer. The detection of analyte ions can be used to indicate thepresence of alpha, beta or gamma irradiation. In an embodiment of theinvention, reactive analyte molecules can be leaked into differentcompartments of a container to increase the probability of GIS detectingionization and an analyzer thereafter analyzing analyte molecules. In anembodiment of the invention, water or ammonia gas or can be leaked intothe container compartments and the detection of for example m/z 19 inthe positive ionization mode or m/z 18 in the positive ionization modeor for example m/z 17 in the negative ionization mode or m/z 16 in thenegative ionization mode can be use to identify a radiological threat.

In an embodiment of the invention, activation of the AISM for analysiscan be facilitated by one or more of the following events (i) providingelectrical power to the atmospheric ionizer; (ii) insertion of asubassembly that permits transfer of gas to the atmospheric ionizer(iii) enclosure of the sorbent material into a chamber. In an embodimentof the invention, enclosure of the sorbent in a chamber can beaccompanied by introduction of a tube to permit transfer of analytemolecules together with carrier gas to a spectroscopy system. In analternative embodiment of the invention, the spectroscopy system can bepositioned in close proximity to the AISM for analysis at the containersite. In another alternative embodiment of the invention, thespectroscopy system can be positioned in close proximity to the samplingtube for analysis at the container site. In another embodiment of theinvention, the AISM can be removed within the chamber and transferred toa remote location for analysis. In another embodiment of the invention,the sorbent material can be removed from the chamber and transferred toa remote location for analysis.

In an embodiment of the invention, after analysis the AISM can bereactivated to allow for a subsequent analysis with the same sorbentsurface. In another embodiment of the invention, the sorbent surface canbe replaced to allow for a subsequent analysis with a new or regeneratedsorbent surface. In an embodiment of the invention, a source of heat canbe used to reactivate the sorbent surface. In an embodiment of theinvention, heated gas from the atmospheric ionizer can be used toreactivate the sorbent surface. In an alternative embodiment of theinvention, a thermoelectric source can be used to heat the sorbentsurface. The heat acts at least by vaporizing residual chemical entitiesfrom the sorbent surface. In an embodiment of the invention, thereactivation of the sorbent surface enables multiple uses of the AIMSwithout requiring its removal from the container thus reducing operatingcost. In an embodiment of the invention, a subassembly mates to the AIMSto effect the reactivation. In an embodiment of the invention, thereactivation can be carried out during insertion of the subassembly. Inanother embodiment of the invention, the reactivation can be completedafter insertion of the subassembly. In an alternative embodiment of theinvention, the reactivation can be carried out after the container isre-filled to reduce the possibility of false (negative or positive)indicators.

While external ion sources are known for use with MS, the problem oftransporting sufficient ions to the MS typically results in loweredsensitivity. The problem is exacerbated with an external ionizationsource operated at or near atmospheric pressure, since the MS typicallyoperates at high vacuum. In one embodiment of the invention, anatmospheric ionizer and a GIS deliver ions to the MS.

In various embodiments of the invention, a GIS comprising two or moreco-axial tubes with a gap between the tubes and a vacuum applied in thegap region is used to allow large volumes of carrier gas to be sampled.In an embodiment of the invention, a GIS is made up of an inlet tube andan outlet tube where the proximal end of the inlet tube is closest tothe atmospheric ionizer and the distal end of the inlet tube can befurthest from the atmospheric ionizer. The standard design of shippingcontainers can be an aide when designing a method of monitoring thecontents of a shipping container. In various embodiments of theinvention, the inlet tube can be assembled integral with the containerduring its construction, where the distal end of the inlet tube can bedirected to the AISM and the proximal end of the inlet tube can bepositioned adjacent to the spectroscopy system where the vacuum can beapplied. In an embodiment of the invention, the outlet tube can belocated within the spectroscopy system and can be used to one or bothpre-concentrate and train the ions formed and flowing through the inlettube of the gas ion separator to enter the spectroscopy system. Inembodiments of the invention, by embedding the inlet tube in thecontainer during construction of the container, the possibility oftampering with or otherwise interfering with the AISM detection systemcan be reduced.

B. Passive Ionization

In an embodiment of the invention, the same equipment used for activeionization can be used in a different conformation to analyze thecontents of a container using passive ionization (i.e., requiring aradioactive nucleus to ionize the analyte molecules. In thisexperimental set up, the tube used to transport analyte molecules to thesorbent material can be used as an inlet tube of a GIS. The outlet tubewould then be a separate tube positioned with an appropriate gapdistance from this inlet tube. In an alternative embodiment of thisinvention, the function of the outlet tube would be performed by theactive ionization inlet tube.

In various embodiments of the invention, the tube contained within thecontainer framework including one or more of the rails, stringers,reinforcing rings and seams (hereinafter the contained tube), used totransfer the atmosphere at remote locations in the container to the areaadjacent to the sorbent surface can also be used as an inlet tube for aGIS. The proximal end of the contained tube exits the containerframework to sample a location in the container. The distal end of thecontained tube exits the container framework at the position where thesorbent material is located. In this embodiment of the invention, thesorbent material is not utilized. The contained tube can act as an inlettube for a GIS. By adjusting an outlet tube close to the distal end ofthe contained tube and applying a vacuum in this region, the outlet tubecan one or both pre-concentrate and transfer ions formed at the locationto a spectrometer. The region where the distal end of the contained tubeexits near the sorbent material, and a vacuum can be applied is referredto as the Passive Ionization Module. By introducing an outlet tubeconnected to a spectroscopy system, where the outlet tube is adjusted tobe in close proximity to the distal end of the contained tube and thenintroducing a vacuum to the region between the outlet tube and thedistal end of the tube, the PIM can be converted into a GIS for samplingpassive ionization occurring in distant locations in the container. Invarious embodiments of the invention, by using a GIS connected to thesedisparate locations in the container, the presence of ions can be usedto infer that a radioactive nucleus is present in the container.

In an embodiment of the invention, a container adapted for detectingradioactive nuclei in the container comprises the container, wherein thecontainer can be substantially confined on all sides, wherein thecontainer includes at least a container distal end and a containerproximal end, wherein the container proximal end has a first atmosphere,wherein the container distal end has a second atmosphere. A passiveionization module (PIM), wherein the PIM is adapted to receive a vacuumto be applied to a region in the PIM, wherein the PIM is adapted toreceive an outlet tube connected to a spectroscopy system. Two tubeslocated in the container, wherein each of the two tubes have a distalend and a proximal end, wherein a distal end is located at the containerdistal end, wherein a distal end is located at the container proximalend, wherein the proximal end of the two tubes are located in the regionin the PIM, wherein when the vacuum and the outlet tube connected to aspectroscopy system is received in the PIM the spectrometer detect ionsformed in one or both the first atmosphere and the second atmosphere.

In an embodiment of the invention, a container adapted for detectingradioactive nuclei in the container comprises the container, wherein thecontainer can be substantially confined on all sides, wherein thecontainer includes at least a container distal end and a containerproximal end, wherein the container proximal end has a first atmosphere,wherein the container distal end has a second atmosphere. A passiveionization module (PIM), wherein the PIM is adapted to receive a vacuumto be applied to a region in the PIM, wherein the PIM is adapted toreceive an outlet tube, wherein the outlet tubes has a proximal end anda distal end, wherein the distal end of the outlet tube is connected toa spectroscopy system, wherein the proximal end of the outlet tube islocated in the regions in the PIM. One or more tubes located in thecontainer, wherein each of the one or more tubes have a distal end and aproximal end, wherein the distal end of the one or more tubes is locatedat one or both the container distal end and the container proximal end,wherein the proximal end of the one or more tubes is located in theregion in the PIM, wherein when the vacuum and the outlet tube connectedto a spectroscopy system is received in the PIM the spectroscopy systemdetects ions formed in one or both the first atmosphere and the secondatmosphere.

In an embodiment of the invention, a container adapted for detectingradioactive nuclei in the container comprises the container, wherein thecontainer can be substantially confined on all sides, wherein thecontainer includes at least a container distal end and a containerproximal end, wherein the container proximal end has a first atmosphere,wherein the container distal end has a second atmosphere. One or morepassive ionization modules (PIMs), wherein each of the one or more PIMsis adapted to receive a vacuum to be applied to one or more regions inthe one or more PIMs, wherein each of the one or more PIMs is adapted toreceive one or more outlet tubes, wherein each of the one or more outlettubes has a proximal end and a distal end, wherein the distal end of theone or more outlet tubes is connected to one or more spectroscopysystems, wherein the proximal end of the one or more outlet tubes islocated in the one or more regions in the one or more PIMs. One or moretubes located in the container, wherein each of the one or more tubeshave a distal end and a proximal end, wherein the distal end of the oneor more tubes is located at one or both the container distal end and thecontainer proximal end, wherein the proximal end of the one or moretubes is located in the one or more regions in the PIMs, wherein whenthe vacuum and the outlet tube connected to a spectroscopy system isreceived in the one or more PIMs the one or more spectroscopy systemsdetect ions formed in one or both the first atmosphere and the secondatmosphere.

A method for detecting the presence of a controlled substance in acontainer, comprises receiving the container including one or moreatmospheric ionization sorbent modules (AISM) containing one or moresorbent surfaces and one or more regions in front of the sorbentsurfaces, wherein the one or more AISM are located one or both withinthe container and outside the container, wherein the one or more AISMare adapted to receive one or more atmospheric ionizers and one or moretubes located in the container connecting one or both the distal end andthe proximal end to the region in front of the sorbent surface. Couplingone or more atmospheric ionizer with the one or more AISM, wherein theone or more atmospheric ionizers are directed at the one or more regionsin front of the sorbent surface, wherein the one or more atmosphericionizers form ions of molecules present in one or both the one or moreregions in front of the one or more sorbent surfaces and on the one ormore sorbent surfaces. Connecting one or more gas ion separator (GIS) inthe one or more regions in front of the sorbent surfaces, wherein theone or more AISM are adapted to receive the one or more GIS. Connectingone or more spectrometers to the one or more GIS, wherein the one ormore GIS transport the ions into the one or more spectroscopy system.Detecting the ions to determine the presence of a controlled substance.

In another embodiment of the invention, a Radio Frequency IDentification(RFID) tag is imbedded in one or more AISM. In one embodiment of theinvention, the RFID tag operates using an Ultra High Frequency (UHF)signal. In another embodiment of the invention, the RFID tag operatesusing a microwave frequency signal. In an embodiment the RFID tag can bepositioned so that the RFID tag antenna is least affected by surroundingmetal.

In one embodiment the RFID tag is read only. In another embodiment, theRFID tag contains an Electrically Erasable Programmable Read-Only Memory(EPROM), which enables both read and write functions. In an embodimentof the invention, the RFID tag is passive. In another embodiment of theinvention, the RFID tag is semi passive containing a source of energysuch as a battery to allow the tag to be constantly powered. In afurther embodiment of the invention, the RFID tag is active, containingan internal power source, such as a battery, which is used to power anyIntegrated Circuit's (ICs) in the tag and generate the outgoing signal.In another embodiment, the tag has the ability to enable locationsensing through a photo sensor.

In one embodiment of the invention, a cellular modem is imbedded in theAISM. The cellular modem can be a Code Division Multiple Access (CDMA)modem. In an embodiment of the invention, a RFID reader and associateintegrated circuit processor are embedded together with the cellularmodem in the AISM. In such an embodiment, the RFID tags and RFID readerare positioned to optimize the RFID read of the RFID tags from the otherAISM in the container.

In an embodiment of the invention, where a RFID reader and a cellularmodem are embedded in the core of one or more of the AISM, the RFIDreader is in communication with one or more of the RFID tags of AISM inthe vicinity of the RFID reader. In an embodiment of the invention, theRFID reader and associate processor are in communication with theembedded cellular modem. In an embodiment of the invention, the cellularmodem is in communication with a base station and can transmit one ormore parameters selected from the group consisting of one or more RFIDtag location, one or more RFID tag identification code, shipmentinformation, analysis information, duration of analysis and time stamp.

In an embodiment of the invention, the microprocessor that monitors theintegrity of the shipping container can transmit an alarm signal throughthe cellular modem thereby silently alerting the shipping agent to theidentity of the contents.

In one embodiment of the invention the RFID code uses the IEEE formatand is Electronic Product Code (EPC) readable. In another embodiment ofthe invention the RFID code uses the UCC format and is Universal ProductCode (UPC) readable. In another embodiment, the format is compatible forEPC, European Article Number (EAN) and UPC read and write functions.

A system for determining the presence of controlled substances whentransporting a cargo for a period of time comprising receiving acontainer for holding the cargo, wherein the container can besubstantially confined on all sides, wherein the container includes oneor more sorbent surface located inside the container, wherein the one ormore sorbent surface is exposed to the atmosphere inside the containerfor at least a portion of the period of time. One or more atmosphericionizer located in the container, wherein the atmospheric ionizerproduces reactive species, wherein the reactive species are directedonto one or more sorbent surface. One or more gas ion separators locatedin the container to transfer analyte ions formed off the sorbent surfaceinto a spectrometer for one or more analysis. One or more spectrometerslocated in the container for detecting analyte ions. Receiving analysisdata from the one or more spectrometer. Correlating the analysis datawith analysis of controlled substances, wherein the correlating can alsoinvolve one or more parameters selected from the group consisting of theperiod of time and the portion of the period of time the sorbentmaterial is exposed.

A system for determining the presence of controlled substances whentransporting a cargo for a period of time comprising receiving acontainer for holding the cargo, wherein the container can besubstantially confined on all sides, wherein the container includes oneor more sorbent surface located inside the container, wherein the one ormore sorbent surface is exposed to the atmosphere inside the containerfor at least a portion of the period of time. One or more gas ionseparators inlet tubes. Receiving an AISM ionizer/analyzer, wherein theAISM ionizer/analyzer can be located to sample the sorbent surfacelocated in the container including one or more atmospheric ionizerwherein the atmospheric ionizer produce reactive species, wherein thereactive species are directed onto one or more sorbent surface. One ormore gas ion separators outlet tubes. A spectrometer for detectinganalyte ions, wherein the one or more gas ion separator inlet tubelocated in the container and the one or more gas ion separator outlettube connect to transfer analyte ions formed off the sorbent surfaceinto the spectrometer for one or more analysis. Receiving analysis datafrom the AISM ionizer/analyzer. Correlating the analysis data withanalysis of controlled substances, wherein the correlating can alsoinvolve one or more parameters selected from the group consisting of theperiod of time and the portion of the period of time the sorbentmaterial is exposed.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein reactive species fromat least one atmospheric ionizer are directed onto one sorbent surface.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein two or more sorbentsurfaces undergo spectrometric analysis to sample different compartmentswithin the container.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time, wherein two or more sorbentsurfaces are analyzed to provide an average analysis representative ofthe contents of the container.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein two or more sorbentsurfaces are analyzed to provide analysis from different compartmentswith the container.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein the sorbent surfacealso contains a chemical code to verify the integrity of the sorbentsurface. The chemical code can be one or more molecules that are stableto oxidation or stable to further oxidation and have sufficiently lowvapor pressure that they remain present on the sorbent surface afterdeposition for a period of approximately 12 months. The chemical codecan be one or more molecules that do not produce ions that can interferewith the analysis of common controlled substances including explosives,radiation threats or illicit drugs. The chemical code can include one ormore polydisperse or monodisperse synthetic organic polymers, paints,dyes, other small (less than approximately 200 Dalton) organic moleculesand other small (less than approximately 200 Dalton) inorganicmolecules. In an embodiment of the invention, the synthetic polymersinclude polyether, polyglycol, polyester, polyethylene,poly(halogen)ethylene, polypropylene, polyvinylidene halogen,polymethylmethacrylate, polyacrylonide, polycaprolactone, polylactide,poly butylene succinate, polybutylene succinate adipate, polybutylenesuccinate terephthalate, poly-hydroxypropionate, poly-hydroxybutyrate,poly-hydroxyvalerate, poly-hydroxyhexanoate, poly-3-hydroxyoctanoate,poly-3-hydroxyphenylvaleric acid and poly-3-hydroxyphenylhexanoic acid.In an embodiment of the invention, the dyes can include one or more dyesselected from the group consisting of methoxycoumarin, coumarins,fluorescein, bodipy-Fl, ethidium bromide, bodipy-R6G, Rhodamine, TAMRA,Cy-3 and Coomassie blue. In an embodiment of the invention, theinorganic molecules include transition metal oxides including FeS, NiO,SiO₂, Ni₂O₃, Al₂O₃, Fe₂O₃ and Fe₃O₄. In an embodiment of the invention,the chemical code is a (0.5:0.01:1:0.1, wt:wt) mixture of monodispersepolystyrene (n=4), Coomassie blue, fructose and Fe₂O₃. The chemical codecan be arranged in a specific pattern on the sorbent surface. Thepattern can be in the form of a bar code so that the chemical codefunctions as both a chemical and physical bar code. In an embodiment ofthe invention, an appropriate wavelength light can be used to scan thesorbent material and a dye which makes up the chemical code can be usedto verify the presence of the chemical code on the sorbent surfacewithout the need to use the spectroscopy system. The system fordetermining the presence of controlled substances when transporting acargo for a period of time containing a sorbent surface with a chemicalcode wherein reactive species from at least one atmospheric ionizer aredirected onto the chemical code of the sorbent surface to verify theintegrity of the sorbent surface.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein two or more sorbentsurfaces are exposed for different portions of the period of time. Thesystem for determining the presence of controlled substances whentransporting a cargo for a period of time, two or more sorbent surfacesare exposed for different portions of the period of time, wherein thetwo or more sorbent surfaces undergo spectrometric analysis and the twoor more analyses are correlated with the different portions of theperiod of time to verify the analysis.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein the temperature of oneor more of the sorbent surfaces is held for at least a portion of theperiod of time at between a lower limit of approximately 1×10² degrees Kand an upper limit of approximately 4×10² degrees K.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein one or more of thesorbent surfaces is regenerated by heating to between a lower limit ofapproximately 3×10² degrees K and an upper limit of approximately 5×10²degrees K.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein one or more of theatmospheric ionizer is activated by connection to two or more utilitiesselected from the group consisting of a source of electrical current, apressurized volume of gas of between a lower limit of approximately 2kPaand an upper limit of 60 kPa and a vacuum pump capable of generating avacuum between a lower limit of approximately 10 torr and an upper limitof approximately 500 torr.

The system for determining the presence of controlled substances whentransporting a cargo for a period of time wherein the spectrometer isselected from the group consisting of an ion mobility spectrometer, amass spectrometer, an infrared spectrometer, a differential mobilityspectrometer, a digital mass spectrometer and a chemical analyzer.

A cargo container detection system that comprising a cargo container.One or more atmospheric ionizer, capable of producing reactive species(RS), wherein one or more of the atmospheric ionizer include a vesselwith an outlet where the RS exit, wherein the one or more atmosphericionizer are locatable to one or more regions in the container, whereinthe plurality of RS that exit the distal tube of the atmospheric ionizerinteract and ionize analyte species (AS) present in the container. Oneour more gas ion separators (GIS) locatable within the container,wherein the plurality of AS enter the proximal end of one or more GISinlet tube and exit the distal end of the GIS inlet tube, wherein theplurality of AS enter the proximal end of one or more GIS outlet tubeand exit the distal end of the GIS outlet tube. One or more spectrometerfor analysis, wherein the one or more spectrometer are locatable to oneor more locations, wherein the plurality of AS that exit the distal endof the GIS outlet tube enter the one or more spectrometer, wherein theAS are detected in the one or more spectrometer.

The cargo container detection system wherein one or more atmosphericionizer is positioned a distance from the proximal end of one or moreGIS inlet tube between a lower limit of approximately 1×10⁻⁶ m and anupper limit of approximately 3×10⁻² m.

The cargo container detection system wherein the distal end of one ormore GIS inlet tube is positioned a distance from the vacuum regionassociated with the one or more spectrometer between a lower limit ofapproximately 1×10⁻⁶ m and an upper limit of approximately 1×10⁻² m.

The cargo container detection system wherein the one or more atmosphericionizer regions are approximately coincident with the one or morespectrometer locations.

The cargo container detection system wherein the air in the container isone or both blown and sucked from one or more regions within thecontainer in to the region around one or more atmospheric ionizer.

The cargo container detection system wherein the RS pass thru one ormore RS tubes, wherein the RS tube has a distal and a proximal end,wherein the RS enter the proximal end and exit the distal end beforeinteracting and ionizing an analyte molecule.

The cargo container detection system the RS pass thru one or more RStubes, wherein one or both the RS tubes and the GIS inlet tubes arebuilt into the substructure of the cargo container.

The cargo container detection system the RS pass thru one or more RStubes, wherein one or both the RS tubes and the GIS inlet tubes are notaccessible from inside the container and outside the container.

The cargo container detection system the RS pass thru one or more RStubes, wherein a sorbent surface is placed at the distal end of the RStubes, wherein the RS exiting the distal end of the RS tubes impinge onthe sorbent surface.

The cargo container detection system wherein a sorbent surface is placedat the distal end of the RS tubes, wherein means for one or both blowingand sucking air is used to recirculate air from one or more regionswithin the container across the sorbent surface.

The cargo container detection system wherein a sorbent surface is placedat the distal end of the RS tubes, wherein the one or more distal end ofRS tubes are located in close proximity to one or more sorbent surfacessufficient to produce one or more AS for detection.

A method for detecting the presence of one or more controlled substancesin a transport container, comprising receiving the container aftertransport of the container, wherein one or more atmospheric ionizationsorbent module (AISM) was installed one or both prior to and duringtransport of the container. Locating one or more atmospheric ionizer onor near the container, wherein the atmospheric ionizer is located suchthat a plurality of reactive species from the one or more atmosphericionizer impinge the one or more AISM, wherein a plurality of analytespecies are formed when the reactive species impinge the one or moreAISM. Locating one or more spectrometers on or near the container,wherein the one or more spectrometers are located such that a pluralityof analyte species formed at the one or more AISM enter the one or morespectrometers. Detecting the analyte species with the one or morespectrometers to determine if one or more controlled substances werepresent in the container.

Example embodiments of the methods, systems, and components of thepresent invention have been described herein. As noted elsewhere, theseexample embodiments have been described for illustrative purposes only,and are not limiting. Other embodiments are possible and are covered bythe invention. Such embodiments will be apparent to persons skilled inthe relevant art(s) based on the teachings contained herein. Forexample, it is envisaged that, irrespective of the actual shape depictedin the various Figures and embodiments described above, the outerdiameter exit of the inlet tube can be tapered or non-tapered and theouter diameter entrance of the outlet tube can be tapered ornon-tapered.

Thus, the breadth and scope of the present invention should not belimited by any of the above-described exemplary embodiments, but shouldbe defined only in accordance with the following claims and theirequivalents.

What is claimed is:
 1. An ionization device comprising: (a) anatmospheric ionization sorbent module including a sorbent material and aheadspace; (b) a device adapted to introduce one or more analytemolecules to the headspace adjacent to the sorbent material; (c) a heatsource adapted to heat the sorbent material; and (d) an atmosphericionizer adapted to direct a plurality of ionizing species at the sorbentmaterial to generate one or more molecule ions of the one or moreanalyte molecules.
 2. The device of claim 1, where in step (b) the oneor more analyte molecules can be absorbed, adsorbed or condensed on thesorbent material.
 3. The device of claim 1, where a thermoelectricsource is used to heat the sorbent material.
 4. The device of claim 1,where the temperature of the sorbent material is controlled by atemperature controller.
 5. The device of claim 1, further comprisingwhere the sorbent material is segmented.
 6. The device of claim 5, wherethe segmented sorbent material collects both low vapor pressuremolecules and high vapor pressure molecules.
 7. The device of claim 5,where a first segment of the sorbent material is analyzed at a firsttemperature and a second segment of the sorbent material is analyzed ata second temperature, where the first temperature is not equal to thesecond temperature.
 8. The device of claim 1, where the temperature ofthe sorbent material is held for a period of time at between: a lowerlimit of approximately 1×10² degrees K; and an upper limit ofapproximately 4×10² degrees K.
 9. The device of claim 1, furthercomprising directed ionizing species generated at different temperaturesat the sorbent material.
 10. The device of claim 1, further comprisingdirected ionizing species generated with different reagent species atthe sorbent material.
 11. A method of ionizing one or more analytemolecules comprising: (a) introducing one or more analyte molecules toan atmospheric ionization sorbent module (AISM), the AISM including asorbent material and a headspace; (b) heating the sorbent material; and(c) directing a plurality of ionizing species at the sorbent material togenerate one or more molecule ions, thereby ionizing the one or moreanalyte molecules.
 12. The method of claim 11, where the one or moreanalyte molecules can be absorbed, adsorbed or condensed on the sorbentmaterial.
 13. The method of claim 11, where the temperature of thesorbent material is controlled by a temperature controller.
 14. Themethod of claim 11, further comprising directed ionizing speciesgenerated at different temperatures at the sorbent material.
 15. Asystem of ionizing one or more analyte molecule comprising: (a) anatmospheric ionization sorbent module (AISM), the AISM including asorbent material and a headspace; (b) a device to introduce one or moreanalyte molecules to the headspace adjacent to the sorbent material; (c)a heat source to heat the sorbent material; and (d) an atmosphericionizer to direct a plurality of ionizing species at the sorbentmaterial to generate one or more molecule ions of the one or moreanalyte molecules.
 16. The system of claim 15, further comprising atemperature controller to control the temperature of the sorbentmaterial.
 17. The system of claim 15, further comprising directedionizing species generated at different temperatures at the sorbentmaterial.
 18. The system of claim 15, further comprising directedionizing species generated with different reagent species at the sorbentmaterial.
 19. The system of claim 15, further comprising where thesorbent material is segmented.
 20. The system of claim 19, where a firstsegment of the sorbent material is analyzed at a first temperature and asecond segment of the sorbent material is analyzed at a secondtemperature, where the first temperature is not equal to the secondtemperature.